Compounds Comprising Triazine Group, Fluorene-Group and Hetero-Fluorene Group

ABSTRACT

suitable for use as a layer material for electronic devices, and to an organic semiconductor layer comprising at least one compound according to formula 1, as well as to an organic electronic device comprising at least one organic semiconductor layer, and a method of manufacturing the same.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to European Patent Application No.17200894.8, filed Nov. 9, 2017, which is incorporated herein byreference.

TECHNICAL FIELD

The present invention relates to compounds, in particular to compoundswith a triazine group, fluorene group and hetero-fluorene group,suitable for use as a layer material for electronic devices, and to anorganic semiconductor layer comprising at least one compound thereof, aswell as to an organic electronic device comprising at least one organicsemiconductor layer, and a method of manufacturing the same.

BACKGROUND ART

Organic electronic devices, such as organic light-emitting diodes OLEDs,which are self-emitting devices, have a wide viewing angle, excellentcontrast, quick response, high brightness, excellent operating voltagecharacteristics, and color reproduction. A typical OLED comprises ananode, a hole transport layer HTL, an emission layer EML, an electrontransport layer ETL, and a cathode, which are sequentially stacked on asubstrate. In this regard, the HTL, the EML, and the ETL are thin filmsformed from organic compounds.

When a voltage is applied to the anode and the cathode, holes injectedfrom the anode move to the EML, via the HTL, and electrons injected fromthe cathode move to the EML, via the ETL. The holes and electronsrecombine in the EML to generate excitons. When the excitons drop froman excited state to a ground state, light is emitted. The injection andflow of holes and electrons should be balanced, so that an OLED havingthe above-described structure has excellent efficiency and/or a longlifetime.

Performance of an organic light emitting diode may be affected bycharacteristics of the organic semiconductor layer, and among them, maybe affected by characteristics of an organic material of the organicsemiconductor layer.

Particularly, development for an organic material being capable ofincreasing electron mobility and simultaneously increasingelectrochemical stability is needed so that the organic electronicdevice, such as an organic light emitting diode, may be applied to alarge-size flat panel display.

WO2017171376 relates to a compound of the chemical formula 1 and anorganic electronic element comprising the compound.

There remains a need to improve performance of organic semiconductorlayers, organic semiconductor materials, as well as organic electronicdevices thereof, in particular to achieve increased lifetime and higherefficiency through improving the characteristics of the compoundscomprised therein.

There is a need for alternative organic semiconductor materials andorganic semiconductor layers as well as organic electronic deviceshaving increased lifetime and/or improved efficiency at low operatingvoltage.

In particular there is a need for alternative compounds having increasedlifetime as well as improved efficiency and at the same time keeping theoperating voltage and thereby the power consumption low to deliver longbattery life for example mobile electronic devices.

DISCLOSURE

An aspect of the present invention provides a compound of formula 1,

-   wherein    -   X is selected from O or S;    -   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or        unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃        to C₃₆ heteroaryl;    -   Ar² is selected from C₁ to C₁₆ alkylene or is selected from        unsubstituted arylene (C7) to (C11):

-   -   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or        unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃        to C₃₆ heteroaryl; and    -   wherein        -   Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃            to C₃₆ heteroaryl is mono or di-substituted, wherein            -   the substituents of the substituted C₆ to C₂₄ aryl and                substituted C₃ to C₃₆ heteroaryl are selected from C₁ to                C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated                C₁ to C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆                alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN;                and    -   wherein        -   Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃            to C₃₆ heteroaryl is mono or di-substituted, wherein

-   the substituents of the substituted C₆ to C₃₆ aryl and substituted    C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆ alkyl, C₁ to C₁₆    alkoxy, partially or perfluorinated C₁ to C₁₆ alkyl, partially or    perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅    heteroaryl, F or CN

According to another embodiment a compound of formula 1, is provided

-   wherein-   X is selected from O or S;-   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;-   Ar² is selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene;-   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;    and-   wherein    -   substituted C₆ to C₂₄ aryl of Ar¹ or substituted C₃ to C₃₆        heteroaryl of Ar¹ is mono or di-substituted; and-   wherein    -   substituted C₆ to C₃₆ aryl of Ar³ or substituted C₃ to C₃₆        heteroaryl of Ar³ is mono or di-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O or S, preferably O;-   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆        alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈        aryl, C₃ to C₂₅ heteroaryl, F or CN, preferably preferably from        C₁ to C₁₆ alkyl;-   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene, wherein    -   the substituents of the substituted C₆ to C₃₆ arylene are        selected from C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially or        perfluorinated C₁ to C₁₆ alkyl, partially or perfluorinated C₁        to C₁₆ alkoxy, F or CN, preferably from C₁ to C₁₆ alkyl;-   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₃₆ arylene and        substituted C₃ to C₃₆ heteroarylene are selected from C₁ to C₁₆        alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆        alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈        aryl, C₃ to C₂₅ heteroaryl, F or CN, preferably from C₁ to C₁₆        alkyl;    -   wherein substituted Ar¹ and/or Ar³ is mono or di-substituted.

The Ar¹ group is connected via a single bond to the triazine group ofthe compound of formula 1. Mono or di-substituted Ar¹ means throughoutthe specification that for mono-substituted Ar¹ the Ar¹ group comprisesone additional substituent and for di-substituted Ar¹ the Ar¹ groupcomprises two additional substituents, which can be independentlyselected.

The Ar³ group is connected via a single bond to a fluorene group of thecompound of formula 1. Mono or di-substituted Ar³ means throughout thespecification that for mono-substituted Ar³ the Ar³ group comprises oneadditional substituent and for di-substituted Ar³ the Ar³ groupcomprises two additional substituents, which can be independentlyselected.

Hetero atoms if not otherwise stated can be individually selected fromN, O, S, B, Si, P, Se, preferably from N, O and S and more preferred isN.

According to one embodiment the compound is represented by formula 1,wherein Ar² selected from carbazolylene is excluded.

According to one embodiment the compound of formula 1,

-   can be further defined, wherein-   X can be selected from O or S;-   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN;-   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene, wherein    -   the substituents of the substituted C₆ to C₃₆ arylene are        selected from C₁ to C₁₆ alkyl or CN;-   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₃₆ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN; and-   wherein    -   substituted C₆ to C₂₄ aryl of Ar¹ or substituted C₃ to C₃₆        heteroaryl of Ar¹ is mono or di-substituted; and-   wherein    -   substituted C₆ to C₃₆ aryl of Ar³ or substituted C₃ to C₃₆        heteroaryl of Ar³ is mono or di-substituted.

According to another embodiment of the compound of formula 1,

-   wherein-   X is selected from O or S, preferably O;-   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or C₁ to C₁₆    alkyl, substituted C₆ to C₂₄ aryl, preferably unsubstituted C₆ to    C₁₈ aryl or C₁ to C₁₆ alkyl, substituted C₆ to C₁₈, and further    preferred unsubstituted C₁₂ to C₁₈ aryl or C₁ to C₆ alkyl    substituted C₁₂ to C₁₈, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN;-   Ar² is selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene, preferably phenylene or biphenylene    and more preferred phenylene, wherein    -   the substituents of the substituted C₆ to C₃₆ arylene are        selected from C₁ to C₁₆ alkyl or CN;-   Ar³ is selected from unsubstituted C₆ to C₂₄ aryl, preferably phenyl    or biphenyl and in addition preferred phenyl, wherein    -   the substituents of the substituted C₆ to C₃₆ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O or S;-   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₂₄ aryl, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl are selected        from C₁ to C₁₆ alkyl or C₆ to C₁₈ aryl;-   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene, wherein    -   the substituents of the substituted C₆ to C₃₆ arylene are        selected from C₁ to C₁₆ alkyl;-   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₃₆ aryl, wherein    -   the substituents of the substituted C₆ to C₃₆ aryl are selected        from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl;-   wherein substituted Ar¹ and/or Ar³ is mono or di-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl;-   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene, wherein the substituents of the    substituted C₆ to C₃₆ arylene are selected from C₁ to C₁₆ alkyl;-   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₃₆ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl;-   wherein substituted Ar¹ and/or substituted Ar³ is mono or    di-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl;-   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene, wherein the substituents of the    substituted C₆ to C₃₆ arylene are selected from C₁ to C₁₆ alkyl;-   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or    unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to    C₃₆ heteroaryl, wherein    -   the substituents of the substituted C₆ to C₃₆ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl;-   wherein substituted Ar¹ and/or substituted Ar³ is mono-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl or    unsubstituted C₆ to C₂₄ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl or    unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O or S;-   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl or    unsubstituted C₆ to C₂₄ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl or    unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or    unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl or    unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or    unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl or    unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or    unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₁₂ aryl or    unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or    unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₁₂ aryl or    unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl;-   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl;-   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl;-   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl;-   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl;-   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene;-   Ar³ can be selected from unsubstituted C₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl;-   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene;-   Ar³ can be selected from unsubstituted C₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₂₄ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₂₄ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S;-   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl;-   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene;-   Ar³ can be selected from unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment, formula 1 may comprises at least about5 to about 16 C₆ aryl rings.

According to another embodiment, formula 1 may comprises at least about5 to about 16 C₆ aryl rings and at least about 1 to about 5 six-memberhetero aryl rings, wherein at least one six-member hetero aryl ring is atriazine and the hetero atoms can be individually selected from N, O, S.

According to an aspect the compound of formula 1 can be used as a matrixmaterial for a dopant material.

According to an aspect the layer material can be an organicsemiconductor layer, which is used for an organic electronic device. Forexample, the organic electronic device can be an OLED or there like.

The compounds represented by formula 1 have strong electron transportcharacteristics to increase charge mobility and/or stability and therebyto improve luminance efficiency, voltage characteristics, and/orlifetime characteristics.

The compounds represented by formula 1 have high electron mobility and alow operating voltage.

The compounds represented by formula 1 and an organic semiconductorlayer consisting or comprising of a compound of formula 1 may benon-emissive.

In the context of the present specification the term “essentiallynon-emissive” or “non-emitting” means that the contribution of thecompound or layer to the visible emission spectrum from the device isless than 10%, preferably less than 5% relative to the visible emissionspectrum. The visible emission spectrum is an emission spectrum with awavelength of about ≥380 nm to about <780 nm.

Preferably, the organic semiconductor layer comprising the compound offormula 1 is essentially non-emissive or non-emitting.

The term “free of”, “does not contain”, “does not comprise” does notexclude impurities which may be present in the compounds prior todeposition. Impurities have no technical effect with respect to theobject achieved by the present invention.

The operating voltage, also named U, is measured in Volt (V) at 10milliAmpere per square centimeter (mA/cm2).

The candela per Ampere efficiency, also named cd/A efficiency, ismeasured in candela per ampere at 10 milliAmpere per square centimeter(mA/cm2).

The external quantum efficiency, also named EQE, is measured in percent(%).

The color space is described by coordinates CIE-x and CIE-y(International Commission on Illumination 1931). For blue emission theCIE-y is of particular importance. A smaller CIE-y denotes a deeper bluecolor.

The highest occupied molecular orbital, also named HOMO, and lowestunoccupied molecular orbital, also named LUMO, are measured in electronvolt (eV).

The term “OLED”, “organic light emitting diode”, “organic light emittingdevice”, “organic optoelectronic device” and “organic light-emittingdiode” are simultaneously used and have the same meaning.

The term “transition metal” means and comprises any element in thed-block of the periodic table, which comprises groups 3 to 12 elementson the periodic table.

The term “group III to VI metal” means and comprises any metal in groupsIII to VI of the periodic table.

As used herein, “weight percent”, “wt.-%”, “percent by weight”, “% byweight”, and variations thereof refer to a composition, component,substance or agent as the weight of that composition, component,substance or agent of the respective electron transport layer divided bythe total weight of the composition thereof and multiplied by 100. It isunderstood that the total weight percent amount of all components,substances or agents of the respective electron transport layer areselected such that it does not exceed 100 wt.-%.

As used herein, “volume percent”, “vol.-%”, “percent by volume”, “% byvolume”, and variations thereof refer to an elemental metal, acomposition, component, substance or agent as the volume of thatelemental metal, component, substance or agent of the respectiveelectron transport layer divided by the total volume of the respectiveelectron transport layer thereof and multiplied by 100. It is understoodthat the total volume percent amount of all elemental metal, components,substances or agents of the respective cathode electrode layer areselected such that it does not exceed 100 vol.-%.

All numeric values are herein assumed to be modified by the term“about”, whether or not explicitly indicated. As used herein, the term“about” refers to variation in the numerical quantity that can occur.

Whether or not modified by the term “about”, the claims includeequivalents to the quantities.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a”, “an”, and “the” include plural referentsunless the content clearly dictates otherwise.

It should be noted that, as used in this specification and the appendedclaims, “*” if not otherwise defined indicates the chemical bondingposition.

The anode electrode and cathode electrode may be described as anodeelectrode/cathode electrode or anode electrode/cathode electrode oranode electrode layer/cathode electrode layer.

According to another aspect, an organic optoelectronic device comprisesan anode layer and a cathode layer facing each other and at least oneorganic semiconductor layer between the anode layer and the cathodelayer, wherein the organic semiconductor layer comprises or consists ofthe compound of formula 1.

According to yet another aspect, a display device comprising the organicelectronic device, which can be an organic optoelectronic device, isprovided.

In the present specification, when a definition is not otherwiseprovided, an “alkyl group” may refer to an aliphatic hydrocarbon group.The alkyl group may refer to “a saturated alkyl group” without anydouble bond or triple bond. The alkyl group may be a linear, cyclic orbranched alkyl group.

The alkyl group may be a C₁ to C₁₆ alkyl group, or preferably a C₁ toC₁₂ alkyl group. More specifically, the alkyl group may be a C₁ to C₁₄alkyl group, or preferably a C₁ to C₁₀ alkyl group or a C₁ to C₆ alkylgroup. For example, a C₁ to C₄ alkyl group comprises 1 to 4 carbons inalkyl chain, and may be selected from methyl, ethyl, propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, and t-butyl.

Specific examples of the alkyl group may be a methyl group, an ethylgroup, a propyl group, an isopropyl group, a butyl group, an isobutylgroup, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, andthe like.

In the present specification, when a definition is not otherwiseprovided, R² can be independently selected from H, C₁ to C₁₆ alkyl, C₆to C₁₈ aryl.

In the present specification “arylene group” may refer to a groupcomprising at least one hydrocarbon aromatic moiety, and all theelements of the hydrocarbon aromatic moiety may have p-orbitals whichform conjugation, for example a phenyl group, a naphtyl group, ananthracenyl group, a phenanthrenyl group, a pyrenyl group, a fluorenylgroup and the like.

The arylene group may include a monocyclic, polycyclic or fused ringpolycyclic (i.e., rings sharing adjacent pairs of carbon atoms)functional group.

The term “heteroarylene” may refer to aromatic heterocycles with atleast one heteroatom, and all the elements of the hydrocarbonheteroaromatic moiety may have p-orbitals which form conjugation. Theheteroatom may be selected from N, O, S, B, Si, P, Se, preferably fromN, O and S.

A heteroarylene ring may comprise at least 1 to 3 heteroatoms.Preferably a heteroarylene ring may comprise at least 1 to 3 heteroatomsindividually selected from N, S and/or 0.

Further preferred in addition to the triazine group of formula 1 atleast one additional heteroaryl/ene ring may comprise at least 1 to 3N-atoms, or at least 1 to 2-N atoms or at least one N-atom.

The term “heteroarylene” as used herewith shall encompass dibenzofurane,dibenzothiopene, pyridine, quinoline, quinazoline, pyrimidine, triazine,benzimidazole, benzothiazole, benzoxazole,benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phenoxazine,benzoacridine, dibenzoacridine and the like.

In the present specification, the single bond refers to a direct bond.

In the present specification, when a definition is not otherwiseprovided, Ar¹ can be independently selected from substituted orunsubstituted C₆-C₂₄ aryl or C₃-C₃₆ heteroaryl, wherein the substituentsof C₆-C₂₄ aryl or C₃-C₃₆ heteroaryl are independently selected fromlinear C₁₋₁₆ alkyl, branched C₃₋₁₆ alkyl, CN.

Preferably Ar¹ can be independently selected from substituted orunsubstituted C₆-C₁₈ aryl or C₃-C₁₇ heteroaryl, wherein the substituentsof C₆-C₁₈ aryl or C₃-C₁₇ heteroaryl are independently selected fromlinear C₁₋₁₆ alkyl, branched C₃₋₁₀ alkyl, CN.

Further preferred, Ar¹ can be independently selected from substituted orunsubstituted C₆-C₁₂ aryl or C₄-C₁₁ heteroaryl, wherein the substituentsof C₆-C₁₂ aryl or C₅-C₁₁ heteroaryl are independently selected fromlinear C₁₋₃ alkyl, branched C₃₋₅ alkyl.

In addition preferred, Ar¹ can be independently selected fromunsubstituted C₆-C₁₂ aryl or C₃-C₁₁ heteroaryl, C₄-C₁₁ heteroaryl orC₅-C₁₁ heteroaryl.

In the present specification, when a definition is not otherwiseprovided, Ar² can be independently selected from C₁ to C₁₆ alkylene,substituted or unsubstituted C₆₋₃₆ arylene; wherein the substituents ofthe C₆₋₃₆ arylene are independently selected from C₁-C₁₆ alkyl, CN.

According to another preferred embodiment the compound according toformula 1 may comprise:

-   -   at least 7 to 25 aromatic rings, preferably at least 8 to 22        aromatic rings, further preferred at least 9 to 20 aromatic        rings, in addition preferred at least 10 to 15 aromatic rings        and more preferred at least 10 to 14 aromatic rings; wherein    -   at least 2 to 5, preferably 3 to 4 or 2 to 3, are heteroaromatic        rings.

According to one embodiment the compound according to formula 1:

-   -   comprises at least about 8 to about 20 aromatic rings,        preferably at least about 9 to about 18 aromatic rings, further        preferred at least about 10 to about 16 aromatic rings, in        addition preferred at least about 11 to about 15 aromatic rings        and more preferred at least about 10 to about 14 aromatic rings;        and/or    -   the compound of formula 1 comprises at least about 2 to about 6,        preferably about 3 to about 5 or about 2 to about 4, hetero        aromatic rings, wherein the hetero atoms can be selected from N,        O, S; and/or    -   comprises at least one fluorene ring and at least one        hetero-fluorene ring, wherein the hetero atoms can be selected        from N, O, S; and/or    -   comprises at least one triazine ring, and preferably at least        two triazine rings.

According to one preferred embodiment the compound according to formula1 may comprises at least about 8 to about 20 aromatic rings, preferablyat least about 9 to 18 aromatic rings, further preferred at least 10 toabout 16 aromatic rings, in addition preferred at least 8 to 15 aromaticrings and more preferred at least about 10 to about 14 aromatic rings,wherein at least one of the aromatic rings is an unsubstituted fivemember ring and at least one of the aromatic rings is a five memberhetero-ring.

According to one preferred embodiment the compound according to formula1 may comprises at least about 8 to about 20 aromatic rings, preferablyat least about 9 to 18 aromatic rings, further preferred at least 10 toabout 16 aromatic rings, in addition preferred at least 8 to 15 aromaticrings and more preferred at least about 10 to about 14 aromatic rings,wherein at least one of the aromatic rings is an unsubstituted fivemember ring and at least one of the aromatic rings is a five memberhetero-ring.

According to a further preferred embodiment the compound of formula 1comprises at least 2 to 7, preferably 2 to 5, or 2 to 3 hetero aromaticrings.

According to a further preferred embodiment the compound of formula 1comprises at least 2 to 7, preferably 2 to 5, or 2 to 3 hetero aromaticrings, wherein at least one of the aromatic rings is a five memberhetero aromatic ring.

According to a further preferred embodiment the compound of formula 1comprises at least 3 to 7, preferably 3 to 6, or 3 to 5 hetero aromaticrings, wherein at least two of the hetero aromatic rings are five memberhetero-aromatic-ring.

According to one embodiment the compound according to formula 1 maycomprise at least 6 to 12 non-hetero aromatic rings and 2 to 3 heteroaromatic rings.

According to one preferred embodiment the compound according to formula1 may comprise at least 7 to 12 non-hetero aromatic rings and 2 to 5hetero aromatic rings.

According to one preferred embodiment the compound according to formula1 may comprise at least 7 to 11 non-hetero aromatic rings and 2 to 3hetero aromatic rings.

The term “C₆-arylene ring” means single C₆-arylene rings and C₆-arylenerings which form condensed ring systems. For example, a naphthalenegroup would be counted as two C₆-arylene rings.

According to another embodiment of formula 1, wherein for Ar¹ and/or Ar³at least one heteroarylene group is selected from dibenzofurane,dibenzothiophene, triazine, quinoline, quinazoline, benzimidazole,benzothiazole, benzoxazole, benzo[4,5]thieno[3,2-d]pyrimidine, acridine,benzoacridine, dibenzoacridine, pyrimidine and pyridine, and ispreferably selected from pyridine, quinoline, dibenzofurane ordibenzothiophene.

According to another embodiment, Ar¹ is selected from C₁ to C₁₆ alkyl,substituted or unsubstituted C₆ to C₂₄ aryl or substituted orunsubstituted C₃ to C₃₆ heteroaryl and Ar³ is selected fromdibenzofurane, dibenzothiophene, triazine, quinoline, quinazoline,benzimidazole, benzothiazole, benzoxazole,benzo[4,5]thieno[3,2-d]pyrimidine, acridine, benzoacridine,dibenzoacridine, pyrimidine and is preferably selected from quinoline,dibenzofurane or dibenzothiophene.

According to another embodiment the compound of formula 1 may have aglass transition temperature Tg of about ≥115° C. and about ≤380° C.,preferably about ≥120° C. and about ≤350° C., further preferred about≥125° C. and about ≤320° C., in addition preferred about ≥125° C. andabout ≤200° C. and also preferred about ≥125° C. and about ≤180° C.

According to another embodiment the compound of formula 1 may have aglass transition temperature Tg of about ≥125° C. and about ≤150° C.

The glass transition temperature is measured under nitrogen and using aheating rate of 10 K per min in a Mettler Toledo DSC 822e differentialscanning calorimeter as described in DIN EN ISO 11357, published inMarch 2010.

Room temperature, also named ambient temperature, is 23° C.

Surprisingly, it was found that the compounds of formula 1 and theinventive organic electronic devices solve the problem underlying thepresent invention by being superior over the organic electroluminescentdevices and compounds known in the art, in particular with respect tocd/A efficiency, also referred to as current efficiency and to lifetime.At the same time the operating voltage is kept at a similar or evenimproved level which is important for reducing power consumption andincreasing battery life, for example of a mobile display device. Highcd/A efficiency is important for high efficiency and thereby increasedbattery life of a mobile device, for example a mobile display device.Long lifetime is important for the longevity of a device.

The inventors have surprisingly found that particular good performancecan be achieved when using the organic electroluminescent device as afluorescent blue device.

The specific arrangements mentioned herein as preferred were found to beparticularly advantageous.

Likewise, some compounds falling within the scope of the broadestdefinition of the present invention have surprisingly be found to beparticularly well performing with respect to the mentioned property ofcd/A efficiency and lifetime. These compounds are discussed herein to beparticularly preferred.

Further an organic optoelectronic device having high efficiency and/orlong lifetime may be realized.

According to one embodiment, the compound according to formula 1, mayhave the formula 1a:

According to another embodiment, the compound according to formula 1,may have the formula 1a:

-   wherein-   X is selected from O or S;-   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;-   Ar² is selected from C₁ to C₁₆ alkylene, substituted or    unsubstituted C₆ to C₃₆ arylene;-   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;    and-   wherein    -   substituted C₆ to C₂₄ aryl of Ar¹ or substituted C₃ to C₃₆        heteroaryl of Ar¹ is mono or di-substituted; and-   wherein    -   substituted C₆ to C₃₆ aryl of Ar³ or substituted C₃ to C₃₆        heteroaryl of Ar³ is mono or di-substituted.

According to another embodiment of the compound according to formula 1may have the formula 1a:

-   wherein-   X is selected from O;-   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or substituted or    unsubstituted C₃ to C₃₆ heteroaryl;-   Ar² is selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ is selected from unsubstituted C₆ to C₃₆ aryl or unsubstituted    C₃ to C₃₆ heteroaryl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl;-   Ar² is selected from unsubstituted C₆ to C₃₆ arylene;-   Ar³ is selected from unsubstituted C₆ to C₃₆ aryl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar¹ is substituted or unsubstituted C₆ to C₁₂ aryl, or substituted    or unsubstituted C₃ to C₁₈ heteroaryl, preferably phenyl or biphenyl    and in addition preferred phenyl, wherein    -   the substituents of the substituted C₆ to C₁₂ aryl and        substituted C₃ to C₁₈ heteroaryl are selected from C₁ to C₁₀        alkyl or CN, preferably from C₁ to C₆ alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar² is substituted or unsubstituted C₆ to C₁₃ arylene, more    preferred phenylene or biphenylene and in addition preferred    phenylene, wherein    -   the substituents of the substituted C₆ to C₁₂ arylene are        selected from C₁ to C₁₀ alkyl or CN, preferably from C₁ to C₆        alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar³ is substituted or unsubstituted C₆ to C₂₄ aryl, preferably    phenyl or biphenyl and in addition preferred phenyl, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl are selected        from C₁ to C₁₀ alkyl or CN, preferably from C₁ to C₆ alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar¹ is selected from substituted or unsubstituted annelated C₆ to    C₂₄ aryl or substituted or unsubstituted annelated C₃ to C₃₆    heteroaryl, wherein    -   the substituents of the substituted annelated C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ annelated heteroaryl are selected from C₁        to C₁₆ alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN,        preferably from C₁ to C₁₆ alkyl, and preferably C₁ to C₃ alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar³ is selected from unsubstituted C₆ to C₂₄ aryl, preferably phenyl    or biphenyl and in addition preferred phenyl; and-   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or C₁ to C₁₆ alkyl    substituted C₆ to C₂₄ aryl.

According to another embodiment of formula 1 and/or formula 1a, whereinAr¹ and A³ are selected different.

According to another embodiment of formula 1 and/or formula 1a,

-   wherein Ar¹ and A³ are independently selected from B1 to B53:-   wherein-   a) B1 to B6 are substituted or unsubstituted non-heteroaryl groups:

-   b) B7 to B16 are substituted or unsubstituted annelated    non-heteroaryl groups:

-   c) B17 to B25 are dibenzofurane/dibenzothiophene group:

-   d) B26 to B28 are unsubstituted pyridine groups:

-   e) B29 to B46 are unsubstituted or substituted hetero arylene    groups:

-   f) B47 to B48 unsubstituted annelated hetero arylene groups:

-   g) B49 and B50 are nitrile substituted phenyl groups

-   h) B51 to B53 are nitrile substituted biphenyl groups

-   wherein    -   the substituent R² is independently selected from H, C₁ to C₁₆        alkyl, C₆ to C₁₈ aryl.

According to another embodiment of formula 1 and/or formula 1a, Ar¹ andAr³ are selected from B1 to B25 and B51 to B53, preferably B1 to B25.

According to another embodiment of formula 1 and/or formula 1a, Ar¹ isselected from B1 to B25 and B51 to B53, preferably is selected from B1to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14,B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to another embodiment of formula 1 and/or formula 1a, Ar³ isselected from B1 to B25 and B51 to B53, preferably is selected from B1to B6, more preferred B1.

According to another embodiment, in compound of formula 1 or 1a,

-   -   Ar¹ is selected from B1 to B25 and B51 to B53, preferably is        selected from B1 to B25, also preferred is selected from B2, B5,        B8, B11, B12, B13, B14, B15, also preferred is selected from B2,        B5, B8, B11, B12, B13; and    -   Ar³ is selected from B1 to B6, preferably is selected from B1.

According to one embodiment, the compound according to formula 1 mayhave the formula 1b:

According to one embodiment, the compound according to formula 1 mayhave the formula 1b:

-   wherein-   X is selected from O or S;-   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;-   Ar² is selected from C₁ to C₁₆ alkylene or is selected from    unsubstituted arylene (C7) to (C11):

further preferred Ar² is selected from unsubstituted arylene C₇, C₉, C₁₀or C₁₁, more preferred Ar² is selected from unsubstituted arylene C₇;

-   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;    and-   wherein    -   Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃ to        C₃₆ heteroaryl is mono or di-substituted, wherein        -   the substituents of the substituted C₆ to C₂₄ aryl and            substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆            alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to            C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆            to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN; and-   wherein    -   Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃ to        C₃₆ heteroaryl is mono or di-substituted, wherein        -   the substituents of the substituted C₆ to C₃₆ aryl and            substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆            alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to            C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆            to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN.

According to another embodiment, in compound of formula 1b, Ar¹ and Ar³are selected from B1 to B25 and B51 to B53, preferably is selected fromB1 to B25.

According to another embodiment, in compound of formula 1b, Ar¹ isselected from B1 to B25 and B51 to B53, preferably is selected from B1to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14,B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to another embodiment, in compound of formula 1b, Ar³ isselected from B1 to B25 and B51 to B53.

According to another embodiment, in compound of formula 1b, Ar³ isselected from phenyl and Ar¹ is selected from B1 to B25 and B51 to B53,preferably is selected from B1 to B25, also preferred is selected fromB2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2,B5, B8, B11, B12, B13.

According to one embodiment, the compound according to formula 1 mayhave the formula 1c:

According to one embodiment, the compound according to formula 1 mayhave the formula 1c:

-   wherein-   X is selected from O or S;-   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;-   Ar² is selected from C₁ to C₁₆ alkylene or is selected from    unsubstituted arylene (C7) to (C11):

further preferred Ar² is selected from unsubstituted arylene C₇, C₉, C₁₀or C₁₁, more preferred Ar² is selected from unsubstituted arylene C₇;

-   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted    C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;    and-   wherein-   Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃ to C₃₆    heteroaryl is mono or di-substituted, wherein    -   the substituents of the substituted C₆ to C₂₄ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆        alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈        aryl, C₃ to C₂₅ heteroaryl, F or CN; and-   wherein-   Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃ to C₃₆    heteroaryl is mono or di-substituted, wherein    -   the substituents of the substituted C₆ to C₃₆ aryl and        substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆        alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆        alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈        aryl, C₃ to C₂₅ heteroaryl, F or CN.

According to another embodiment, in compound of formula 1c, Ar¹ and Ar³are selected from B1 to B25 and B51 to B53, preferably are selected fromB1 to B25.

According to another embodiment, in compound of formula 1c, Ar¹ isselected from B1 to B25 and B51 to B53, preferably is selected from B1to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14,B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to another embodiment, in compound of formula 1c, Ar³ isselected from B1 to B25 and B51 to B53.

According to another embodiment, in compound of formula 1c, Ar³ isselected from phenyl and Ar¹ is selected from B1 to B25 and B51 to B53,preferably is selected from B1 to B25, also preferred is selected fromB2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2,B5, B8, B11, B12, B13.

According to one embodiment of the compound according to formula 1, Ar²may be selected from C₁ to C₁₈:

andpreferably Ar² is selected from C₆ to C₁₄, further preferred Ar² isselected from C₇ to C₁₁ and more preferred from C₇.

According to another embodiment the compound of formula 1 can beselected from a compound of D1 to D11:

Anode

A material for the anode may be a metal or a metal oxide, or an organicmaterial, preferably a material with work function above about 4.8 eV,more preferably above about 5.1 eV, most preferably above about 5.3 eV.Preferred metals are noble metals like Pt, Au or Ag, preferred metaloxides are transparent metal oxides like ITO or IZO which may beadvantageously used in bottom-emitting OLEDs having a reflectivecathode.

In devices comprising a transparent metal oxide anode or a reflectivemetal anode, the anode may have a thickness from about 50 nm to about100 nm, whereas semitransparent metal anodes may be as thin as fromabout 5 nm to about 15 nm, and non-transparent metal anodes may have athickness from about 15 nm to about 150 nm.

Hole Injection Layer (HIL)

The hole injection layer may improve interface properties between theanode and an organic material used for the hole transport layer, and isapplied on a non-planarized anode and thus may planarize the surface ofthe anode. For example, the hole injection layer may include a materialhaving a median value of the energy level of its highest occupiedmolecular orbital (HOMO) between the work function of the anode materialand the energy level of the HOMO of the hole transport layer, in orderto adjust a difference between the work function of the anode and theenergy level of the HOMO of the hole transport layer.

When the hole transport region comprises a hole injection layer 36, thehole injection layer may be formed on the anode by any of a variety ofmethods, for example, vacuum deposition, spin coating, casting,Langmuir-Blodgett (LB) method, or the like.

When hole injection layer is formed using vacuum deposition, vacuumdeposition conditions may vary depending on the material that is used toform the hole injection layer, and the desired structure and thermalproperties of the hole injection layer to be formed and for example,vacuum deposition may be performed at a temperature of about 100° C. toabout 500° C., a pressure of about 10⁻⁶ Pa to about 10⁻¹ Pa, and adeposition rate of about 0.1 to about 10 nm/sec, but the depositionconditions are not limited thereto.

When the hole injection layer is formed using spin coating, the coatingconditions may vary depending on the material that is used to form thehole injection layer, and the desired structure and thermal propertiesof the hole injection layer to be formed. For example, the coating ratemay be in the range of about 2000 rpm to about 5000 rpm, and atemperature at which heat treatment is performed to remove a solventafter coating may be in a range of about 80° C. to about 200° C., butthe coating conditions are not limited thereto.

The hole injection layer may further comprise a p-dopant to improveconductivity and/or hole injection from the anode.

p-Dopant

In another aspect, the p-dopant may be homogeneously dispersed in thehole injection layer.

In another aspect, the p-dopant may be present in the hole injectionlayer in a higher concentration closer to the anode and in a lowerconcentration closer to the cathode.

The p-dopant may be one of a quinone derivative or a radialene compoundbut not limited thereto. Non-limiting examples of the p-dopant arequinone derivatives such as tetracyanoquinonedimethane (TCNQ),2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ),4,4′,4″-((1E,1′E,1″E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))-tris(2,3,5,6-tetrafluorobenzonitrile).

Hole Transport Layer (HTL)

Conditions for forming the hole transport layer and the electronblocking layer may be defined based on the above-described formationconditions for the hole injection layer.

A thickness of the hole transport part of the charge transport regionmay be from about 10 nm to about 1000 nm, for example, about 10 nm toabout 100 nm. When the hole transport part of the charge transportregion comprises the hole injection layer and the hole transport layer,a thickness of the hole injection layer may be from about 10 nm to about1000 nm, for example about 10 nm to about 100 nm and a thickness of thehole transport layer may be from about 5 nm to about 200 nm, for exampleabout 10 nm to about 150 nm. When the thicknesses of the hole transportpart of the charge transport region, the HIL, and the HTL are withinthese ranges, satisfactory hole transport characteristics may beobtained without a substantial increase in operating voltage.

Hole transport matrix materials used in the hole transport region arenot particularly limited. Preferred are covalent compounds comprising aconjugated system of at least 6 delocalized electrons, preferablyorganic compounds comprising at least one aromatic ring, more preferablyorganic compounds comprising at least two aromatic rings, even morepreferably organic compounds comprising at least three aromatic rings,most preferably organic compounds comprising at least four aromaticrings. Typical examples of hole transport matrix materials which arewidely used in hole transport layers are polycyclic aromatichydrocarbons, triarylene amine compounds and heterocyclic aromaticcompounds. Suitable ranges of frontier orbital energy levels of holetransport matrices useful in various layer of the hole transport regionare well-known. In terms of the redox potential of the redox couple HTLmatrix/cation radical of the HTL matrix, the preferred values (ifmeasured for example by cyclic voltammetry against ferrocene/ferroceniumredox couple as reference) may be in the range 0.0-1.0 V, morepreferably in the range 0.2-0.7 V, even more preferably in the range0.3-0.5 V.

Buffer Layer

The hole transport part of the charge transport region may furtherinclude a buffer layer.

Buffer layer that can be suitable used are disclosed in U.S. Pat. Nos.6,140,763, 6,614,176 and in US2016/248022.

The buffer layer may compensate for an optical resonance distance oflight according to a wavelength of the light emitted from the EML, andthus may increase efficiency.

Emission Layer (EML)

The emission layer may be formed on the hole transport region by usingvacuum deposition, spin coating, casting, LB method, or the like. Whenthe emission layer is formed using vacuum deposition or spin coating,the conditions for deposition and coating may be similar to those forthe formation of the hole injection layer, though the conditions for thedeposition and coating may vary depending on the material that is usedto form the emission layer. The emission layer may include an emitterhost (EML host) and an emitter dopant (further only emitter).

A thickness of the emission layer may be about 100 Å to about 1000 Å,for example about 200 Å to about 600 Å. When the thickness of theemission layer is within these ranges, the emission layer may haveimproved emission characteristics without a substantial increase inoperating voltage.

Emitter Host

According to another embodiment, the emission layer comprises compoundof formula 1 as emitter host.

The emitter host compound has at least three aromatic rings, which areindependently selected from carbocyclic rings and heterocyclic rings.

Other compounds that can be used as the emitter host is an anthracenematrix compound represented by formula 400 below:

In formula 400, Ar₁₁₁ and Ar₁₁₂ may be each independently a substitutedor unsubstituted C₆-C₆₀ arylene group; Ar₁₁₃ to Ar₁₁₆ may be eachindependently a substituted or unsubstituted C₁-C₁₀ alkyl group or asubstituted or unsubstituted C₆-C₆₀ arylene group; and g, h, i, and jmay be each independently an integer from 0 to 4.

In some embodiments, Ar₁₁₁ and Ar₁₁₂ in formula 400 may be eachindependently one of a phenylene group, a naphthalene group, aphenanthrenylene group, or a pyrenylene group; or a phenylene group, anaphthalene group, a phenanthrenylene group, a fluorenyl group, or apyrenylene group, each substituted with at least one of a phenyl group,a naphthyl group, or an anthryl group.

In formula 400, g, h, i, and j may be each independently an integer of0, 1, or 2.

In formula 400, Ar₁₁₃ to Ar₁₁₆ may be each independently one of

-   -   a C₁-C₁₀ alkyl group substituted with at least one of a phenyl        group, a naphthyl group, or an anthryl group;    -   a phenyl group, a naphthyl group, an anthryl group, a pyrenyl        group, a phenanthrenyl group, or a fluorenyl group;    -   a phenyl group, a naphthyl group, an anthryl group, a pyrenyl        group, a phenanthrenyl group, or a fluorenyl group, each        substituted with at least one of a deuterium atom, a halogen        atom, a hydroxyl group, a cyano group, a nitro group, an amino        group, an amidino group, a hydrazine group, a hydrazone group, a        carboxyl group or a salt thereof,    -   a sulfonic acid group or a salt thereof, a phosphoric acid group        or a salt thereof,    -   a C₁-C₆₀ alkyl group, a C₂-C₆₀ alkenyl group, a C₂-C₆₀ alkynyl        group, a C₁-C₆₀ alkoxy group, a phenyl group, a naphthyl group,        an anthryl group, a pyrenyl group, a phenanthrenyl group, or    -   a fluorenyl group

or

-   -   formulas 7 or 8

Wherein in the formulas 7 and 8, X is selected form an oxygen atom and asulfur atom, but embodiments of the invention are not limited thereto.

In the formula 7, any one of R₁₁ to R₁₄ is used for bonding to Ar₁₁₁.R₁₁ to R₁₄ that are not used for bonding to Ar₁₁₁ and R₁₅ to R₂₀ are thesame as R₁ to R₈.

In the formula 8, any one of R₂₁ to R₂₄ is used for bonding to Ar₁₁₁.R₂₁ to R₂₄ that are not used for bonding to Ar₁₁₁ and R₂₅ to R₃₀ are thesame as R₁ to R₈.

Preferably, the EML host comprises between one and three heteroatomsselected from the group consisting of N, O or S. More preferred the EMLhost comprises one heteroatom selected from S or O.

Emitter Dopant

The dopant is mixed in a small amount to cause light emission, and maybe generally a material such as a metal complex that emits light bymultiple excitation into a triplet or more. The dopant may be, forexample an inorganic, organic, or organic/inorganic compound, and one ormore kinds thereof may be used.

The emitter may be a red, green, or blue emitter.

The dopant may be a fluorescent dopant, for example ter-fluorene, thestructures are shown below. 4.4′-bis(4-diphenyl amiostyryl)biphenyl(DPAVBI, 2,5,8,11-tetra-tert-butyl perylene (TBPe), and Compound 8 beloware examples of fluorescent blue dopants.

The dopant may be a phosphorescent dopant, and examples of thephosphorescent dopant may be an organic metal compound comprising Ir,Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combinationthereof. The phosphorescent dopant may be, for example a compoundrepresented by formula Z, but is not limited thereto:

J₂MX  (Z).

In formula Z, M is a metal, and J and X are the same or different, andare a ligand to form a complex compound with M.

The M may be, for example Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co,Ni, Ru, Rh, Pd or a combination thereof, and the J and X may be, forexample a bidendate ligand.

Electron Transport Layer (ETL)

According to another embodiment, the organic semiconductor layer thatcomprises a compound of formula 1 is an electron transport layer. Inanother embodiment the electron transport layer may consist of acompound of formula 1.

For example, an organic light emitting diode according to an embodimentof the present invention comprises at least one electron transportlayer, and in this case, the electron transport layer comprises acompound of formula 1, or preferably of at least one compound offormulae D1 to D11.

In another embodiment, the organic electronic device comprises anelectron transport region of a stack of organic layers formed by two ormore electron transport layers, wherein at least one electron transportlayer comprises a compound of formula 1.

The electron transport layer may include one or two or more differentelectron transport compounds.

According to another embodiment, a second electron transport layercomprises at least one compound of formula 1 according to the inventionand a first electron transport layer comprises a matrix compound, whichis selected different to the compound of formula 1 according to theinvention, and may be selected from:

-   -   an anthracene based compound or a hetero substituted anthracene        based compound, preferably        2-(4-(9,10-di(naphthalen-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole        and/or        N4,N4″-di(naphthalen-1-yl)-N4,N4″-diphenyl-[1,1′:4′,1″-terphenyl]-4,4″-diamine.

According to another embodiment, a first electron transport layercomprises at least one compound of formula 1 according to the inventionand a second electron transport layer comprises a matrix compound, whichis selected different to the compound of formula 1 according to theinvention, and may be selected from:

-   -   a phosphine oxide based compound, preferably        (3-(dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide        and/or phenyl bis(3-(pyren-1-yl)phenyl)phosphine oxide and/or        3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:1′,2′-f]phosphepine-3-oxide;        or    -   a substituted phenanthroline compound, preferably        2,4,7,9-tetraphenyl-1,10-phenanthroline or        2,9-di(biphenyl-4-yl)-4,7-diphenyl-1,10-phenanthroline.

According to another embodiment a first electron transport layercomprises at least one compound of formula 1 according to the inventionand a second electron transport layer comprises a matrix compound, whichis selected different to the compound of formula 1 according to theinvention, and may be selected from a phosphine oxide based compound,preferably (3-(dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxideand/or phenyl bis(3-(pyren-1-yl)phenyl)phosphine oxide and/or3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:1′,2′-f]phosphepine-3-oxide.

According to another embodiment, a first and a second electron transportlayers comprise a compound of formula 1, wherein the compound of formula1 is not selected the same.

The thickness of the first electron transport layer may be from about0.5 nm to about 100 nm, for example about 2 nm to about 40 nm. When thethickness of the first electron transport layer is within these ranges,the first electron transport layer may have improved electron transportability without a substantial increase in operating voltage.

A thickness of an optional second electron transport layer may be about1 nm to about 100 nm, for example about 2 nm to about 20 nm. When thethickness of the electron transport layer is within these ranges, theelectron transport layer may have satisfactory electron transportingability without a substantial increase in operating voltage.

The electron transport layer may further comprise an alkali halideand/or alkali organic complex.

According to another embodiment, the first and second electron transportlayers comprise a compound of formula 1, wherein the second electrontransport layer further comprises an alkali halide and/or alkali organiccomplex.

Alkali Halide

Alkali halides, also known as alkali metal halides, are the family ofinorganic compounds with the chemical formula MX, where M is an alkalimetal and X is a halogen.

M can be selected from Li, Na, Potassium, Rubidium and Cesium.

X can be selected from F, Cl, Br and J.

According to various embodiments of the present invention a lithiumhalide may be preferred. The lithium halide can be selected from thegroup comprising LiF, LiCl, LiBr and LiJ. However, most preferred isLiF.

The alkali halide is essentially non-emissive or non-emissive.

Alkali Organic Complex

The alkali organic complex comprises an alkali metal and at least oneorganic ligand. The alkali metal is preferably selected from lithium.

According to various embodiments of the present invention the organicligand of the lithium organic complex is a quinolate, a borate, aphenolate, a pyridinolate or a Schiff base ligand;

-   -   preferably the lithium quinolate complex has the formula III, IV        or V:

-   wherein    -   A₁ to A₆ are same or independently selected from CH, CR, N and        O;    -   R is same or independently selected from hydrogen, halogen,        alkyl or arylene or heteroarylene with 1 to 20 carbon atoms; and        more preferred A1 to A6 are CH;    -   preferably the borate based organic ligand is a        tetra(1H-pyrazol-1-yl)borate;    -   preferably the phenolate is a 2-(pyridin-2-yl)phenolate, a        2-(diphenylphosphoryl)phenolate, an imidazol phenolates, or        2-(pyridin-2-yl)phenolate and more preferred        2-(l-phenyl-1H-benzo[d]imidazol-2-yl)phenolate;    -   preferably the pyridinolate is a        2-(diphenylphosphoryl)pyridin-3-olate.

According to various embodiments of the present invention the organicligand of the alkali organic complex, preferably of a lithium organiccomplex, can be a quinolate. Quinolates that can be suitable used aredisclosed in WO 2013079217 A1 and incorporated by reference.

According to various embodiments of the present invention the organicligand of the lithium organic complex can be a borate based organicligand, Preferably the lithium organic complex is a lithiumtetra(1H-pyrazol-1-yl)borate. Borate based organic ligands that can besuitable used are disclosed in WO 2013079676 A1 and incorporated byreference.

According to various embodiments of the present invention the organicligand of the lithium organic complex can be a phenolate ligand,Preferably the lithium organic complex is a lithium2-(diphenylphosphoryl)phenolate. Phenolate ligands that can be suitableused are disclosed in WO 2013079678 A1 and incorporated by reference.

Further, phenolate ligands can be selected from the group ofpyridinolate, preferably 2-(diphenylphosphoryl)pyridin-3-olate. Pyridinephenolate ligands that can be suitable used are disclosed in JP2008195623 and incorporated by reference.

In addition, phenolate ligands can be selected from the group ofimidazol phenolates, preferably2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolate. Imidazol phenolateligands that can be suitable used are disclosed in JP 2001291593 andincorporated by reference.

Also, phenolate ligands can be selected from the group of oxazolphenolates, preferably 2-(benzo[d]oxazol-2-yl)phenolate. Oxazolphenolate ligands that can be suitable used are disclosed in US20030165711 and incorporated by reference.

The alkali organic complex may be essentially non-emissive.

Electron Injection Layer (EIL)

According to another aspect of the invention, the organicelectroluminescent device may further comprise an electron injectionlayer between the electron transport layer (first-ETL) and the cathode.

The electron injection layer (EIL) may facilitate injection of electronsfrom the cathode.

According to another aspect of the invention, the electron injectionlayer comprises:

-   (i) an electropositive metal selected from alkali metals, alkaline    earth metals and rare earth metals in substantially elemental form,    preferably selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Eu and    Yb, more preferably from Li, Na, Mg, Ca, Sr and Yb, even more    preferably from Li and Yb, most preferably Yb; and/or-   (ii) an alkali metal complex and/or alkali metal salt, preferably    the Li complex and/or salt, more preferably a Li quinolinolate, even    more preferably a lithium 8-hydroxyquinolinolate, most preferably    the alkali metal salt and/or complex of the second electron    transport layer (second-ETL) is identical with the alkali metal salt    and/or complex of the injection layer. The electron injection layer    may include at least one selected from LiF, NaCl, CsF, Li₂O, and    BaO.

A thickness of the EIL may be from about 0.1 nm to about 10 nm, or about0.3 nm to about 9 nm. When the thickness of the electron injection layeris within these ranges, the electron injection layer may havesatisfactory electron injection ability without a substantial increasein operating voltage.

The electron injection layer may comprise a compound of formula 1.

Cathode

A material for the cathode may be a metal, an alloy, or an electricallyconductive compound that have a low work function, or a combinationthereof. Specific examples of the material for the cathode may belithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li),calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), silver(Ag) etc. In order to manufacture a top-emission light-emitting devicehaving a reflective anode deposited on a substrate, the cathode may beformed as a light-transmissive electrode from, for example, indium tinoxide (ITO), indium zinc oxide (IZO) or silver (Ag).

In devices comprising a transparent metal oxide cathode or a reflectivemetal cathode, the cathode may have a thickness from about 50 nm toabout 100 nm, whereas semitransparent metal cathodes may be as thin asfrom about 5 nm to about 15 nm.

Substrate

A substrate may be further disposed under the anode or on the cathode.The substrate may be a substrate that is used in a general organic lightemitting diode and may be a glass substrate or a transparent plasticsubstrate with strong mechanical strength, thermal stability,transparency, surface smoothness, ease of handling, and waterresistance.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. However, the present disclosure is not limited tothe following examples.

DESCRIPTION OF THE DRAWINGS

These and/or other aspects and advantages of the present invention willbecome apparent and more readily appreciated from the followingdescription of the exemplary embodiments, taken in conjunction with theaccompanying drawings, of which:

FIG. 1 is a schematic sectional view of an organic light-emitting diode(OLED), according to an exemplary embodiment of the present inventionwith an emission layer, one electron transport layer and an electroninjection layer;

FIG. 2 is a schematic sectional view of an organic light-emitting diode(OLED), according to an exemplary embodiment of the present inventionwith an emission layer and two electron transport layers;

FIG. 3 is a schematic sectional view of an OLED, according to anexemplary embodiment of the present invention with an emission layer andthree electron transport layers;

FIG. 4 is a schematic sectional view of an organic light-emitting diode(OLED), according to an exemplary embodiment of the present inventionwith an emission layer and one electron transport layer;

FIG. 5 is a schematic sectional view of an organic light-emitting diode(OLED), according to an exemplary embodiment of the present inventionwith an emission layer and two electron transport layers;

FIG. 6 is a schematic sectional view of an OLED, according to anexemplary embodiment of the present invention with an emission layer andthree electron transport layers.

Reference will now be made in detail to the exemplary aspects, examplesof which are illustrated in the accompanying drawings, wherein likereference numerals refer to the like elements throughout. The exemplaryembodiments are described below, in order to explain the aspects, byreferring to the figures.

Herein, when a first element is referred to as being formed or disposed“on” a second element, the first element can be disposed directly on thesecond element, or one or more other elements may be disposed therebetween. When a first element is referred to as being formed or disposed“directly on” a second element, no other elements are disposed therebetween.

The term “contacting sandwiched” refers to an arrangement of threelayers whereby the layer in the middle is in direct contact with the twoadjacent layers.

The organic light emitting diodes according to an embodiment of thepresent invention may include a hole transport region; an emissionlayer; and a first electron transport layer comprising a compoundaccording to formula 1.

FIG. 1 is a schematic sectional view of an organic light-emitting diode100, according to an exemplary embodiment of the present invention. TheOLED 100 comprises an emission layer 150, an electron transport layer(ETL) 161 comprising a compound of formula 1 and an electron injectionlayer 180, whereby the first electron transport layer 161 is disposeddirectly on the emission layer 150 and the electron injection layer 180is disposed directly on the first electron transport layer 161.

FIG. 2 is a schematic sectional view of an organic light-emitting diode100, according to an exemplary embodiment of the present invention. TheOLED 100 comprises an emission layer 150 and an electron transport layerstack (ETL) 160 comprising a first electron transport layer 161comprising a compound of formula 1 and a second electron transport layer162, whereby the second electron transport layer 162 is disposeddirectly on the first electron transport layer 161. Alternatively, theelectron transport layer stack (ETL) 160 comprises a first electrontransport layer 161 and a second electron transport layer 162 comprisingcompound of formula 1, whereby the second electron transport layer 162is disposed directly on the first electron transport layer 161.

FIG. 3 is a schematic sectional view of an organic light-emitting diode100, according to an exemplary embodiment of the present invention. TheOLED 100 comprises an emission layer 150 and an electron transport layerstack (ETL) 160 comprising a first electron transport layer 161 thatcomprises a compound of formula 1, a second electron transport layer 162that comprises a compound of formula 1 but different to the compound ofthe first electron transport layer, and a third electron transport layer163, whereby the second electron transport layer 162 is disposeddirectly on the first electron transport layer 161 and the thirdelectron transport layer 163 is disposed directly on the first electrontransport layer 162.

FIG. 4 is a schematic sectional view of an organic light-emitting diode100, according to an exemplary embodiment of the present invention. TheOLED 100 comprises a substrate 110, a first anode electrode 120, a holeinjection layer (HIL) 130, a hole transport layer (HTL) 140, an emissionlayer (EML) 150, one first electron transport layer (ETL) 161, anelectron injection layer (EIL) 180, and a cathode electrode 190. Thefirst electron transport layer (ETL) 161 comprises a compound of formula1 and optionally an alkali halide or alkali organic complex. Theelectron transport layer (ETL) 161 is formed directly on the EML 150.

FIG. 5 is a schematic sectional view of an organic light-emitting diode100, according to an exemplary embodiment of the present invention. TheOLED 100 comprises a substrate 110, a first anode electrode 120, a holeinjection layer (HIL) 130, a hole transport layer (HTL) 140, an emissionlayer (EML) 150, an electron transport layer stack (ETL) 160, anelectron injection layer (EIL) 180, and a cathode electrode 190. Theelectron transport layer (ETL) 160 comprises a first electron transportlayer 161 and a second electron transport layer 162, wherein the firstelectron transport layer is arranged near to the anode (120) and thesecond electron transport layer is arranged near to the cathode (190).The first and/or the second electron transport layer comprise a compoundof formula 1 and optionally an alkali halide or alkali organic complex.

FIG. 6 is a schematic sectional view of an organic light-emitting diode100, according to an exemplary embodiment of the present invention. TheOLED 100 comprises a substrate 110, a first anode electrode 120, a holeinjection layer (HIL) 130, a hole transport layer (HTL) 140, an emissionlayer (EML) 150, an electron transport layer stack (ETL) 160, anelectron injection layer (EIL) 180, and a second cathode electrode 190.The electron transport layer stack (ETL) 160 comprises a first electrontransport layer 161, a second electron transport layer 162 and a thirdelectron transport layer 163. The first electron transport layer 161 isformed directly on the emission layer (EML) 150. The first, secondand/or third electron transport layer comprise a compound of formula 1that is different for each layer, and optionally an alkali halide oralkali organic complex.

Organic Semiconductor Layer

According to another aspect an organic semiconductor layer may comprisesat least one compound of formula 1 and/or formula 1a.

According to one embodiment the organic semiconductor layer maycomprises at least one compound of formula 1 and further comprises ametal, metal salt or organic alkali metal complex, preferably alkalimetal complex, more preferably LiQ or alkali borate.

According to one embodiment, wherein at least one organic semiconductorlayer is arranged between the emission layer and the cathode, preferablybetween the auxiliary electron transport layer and the cathode.

In another embodiment, the organic semiconductor layer is arrangedbetween the emission layer and the electron transport layer.

According to one embodiment, the organic semiconductor layer is arrangedbetween the first and second emission layer. The organic semiconductorlayer can be an electron transport layer, an emission layer, a holeblocking layer, a charge generation layer and/or an electron injectionlayer, preferably an electron transport layer or a charge generationlayer, and more preferred an electron transport layer.

According to one embodiment, the organic semiconductor layer can bearranged between a photoactive layer and a cathode layer, preferablybetween an emission layer or light-absorbing layer and the cathodelayer, preferably the organic semiconductor layer is an electrontransport layer.

According to one embodiment, the organic semiconductor layer maycomprise at least one alkali halide or alkali organic complex.

An organic semiconductor layer comprises a compound according to formula1 or 1a is essentially non-emissive or non-emitting.

Organic Electronic Device

An organic electronic device according to the invention comprises atleast one organic semiconductor layer, wherein at least one organicsemiconductor layer comprises a compound according to formula 1 or 1a.

An organic electronic device according to one embodiment, whichcomprises at least one organic semiconductor layer that comprises acompound according to formula 1 or 1a, wherein this layer is essentiallynon-emissive or non-emitting.

According to one embodiment, the organic electronic device may comprisesat least one organic semiconductor layer comprising a compound offormula 1 and/or 1a that is an electron transport layer, an emissionlayer, a hole blocking layer, a charge generation layer and/or anelectron injection layer, preferably an electron transport layer or acharge generation layer, more preferred an electron transport layer.

An organic electronic device according to one embodiment may include asubstrate, an anode layer, an organic semiconductor layer comprising acompound of formula 1 and/or 1a, and a cathode layer.

The organic electronic device according to according to one embodimentmay comprises at least one organic semiconductor layer, wherein theorganic semiconductor layer comprising a compound of formula 1 and/or 1ais arranged between a photoactive layer and a cathode layer, preferablybetween an emission layer or light-absorbing layer and the cathodelayer, preferably the organic semiconductor layer is an electrontransport layer

The organic electronic device according to according to one embodimentmay comprises at least one organic semiconductor layer comprising acompound of formula 1 and/or 1a, wherein the at least one organicsemiconductor layer further comprises at least one alkali halide oralkali organic complex.

An organic electronic device according to one embodiment comprises atleast one organic semiconductor layer comprising at least one compoundof formula 1 and/or 1a, at least one anode layer, at least one cathodelayer and at least one emission layer, wherein the organic semiconductorlayer comprising at least one compound of formula 1 and/or 1a ispreferably arranged between the emission layer and the cathode layer.

An organic electronic device according to one embodiment comprises atleast one organic semiconductor layer comprising at least one compoundof formula 1 and/or 1a and further comprises at least one alkali halideor alkali organic complex.

An organic electronic device according to one embodiment comprises atleast one organic semiconductor layer, at least one anode layer, atleast one cathode layer and at least one emission layer, wherein theorganic semiconductor layer comprising at least one compound of formula1 and/or 1a is preferably arranged between the emission layer and thecathode layer. Preferably the at least one organic semiconductor layeris an electron transport layer.

An organic light-emitting diode (OLED) according to the invention mayinclude an anode, a hole transport layer (HTL), an emission layer (EML),an electron transport layer (ETL) comprising at least one compound offormula 1 and/or 1a, and a cathode, which are sequentially stacked on asubstrate. In this regard, the HTL, the EML, and the ETL are thin filmsformed from organic compounds.

An organic electronic device according to one embodiment can be a lightemitting device, thin film transistor, a battery, a display device or aphotovoltaic cell, and preferably a light emitting device. A lightemitting device can be an OLED.

According to one embodiment the OLED may have the following layerstructure, wherein the layers having the following order:

an anode layer, a hole injection layer, optional a first hole transportlayer, optional a second hole transport layer, an emission layer, anelectron transport layer comprising a compound of formula 1 according tothe invention, an electron injection layer, and a cathode layer.

According to another aspect of the present invention, there is provideda method of manufacturing an organic electronic device, the methodusing:

-   -   at least one deposition source, preferably two deposition        sources and more preferred at least three deposition sources.

The methods for deposition that can be suitable comprise:

-   -   deposition via vacuum thermal evaporation;    -   deposition via solution processing, preferably the processing is        selected from spin-coating, printing, casting; and/or    -   slot-die coating.

According to various embodiments of the present invention, there isprovided a method using:

-   -   a first deposition source to release the compound of formula 1        according to the invention, and    -   a second deposition source to release the alkali halide or        alkali organic complex, preferably a lithium halide or lithium        organic complex;        the method comprising the steps of forming the electron        transport layer stack; whereby for an organic light-emitting        diode (OLED):    -   the first electron transport layer is formed by releasing the        compound of formula 1 according to the invention from the first        deposition source and the alkali halide or alkali organic        complex, preferably a lithium halide or lithium organic complex        from the second deposition source.

According to various embodiments of the present invention, the methodmay further include forming on the anode electrode an emission layer andat least one layer selected from the group consisting of forming a holeinjection layer, forming a hole transport layer, or forming a holeblocking layer, between the anode electrode and the first electrontransport layer.

According to various embodiments of the present invention, the methodmay further include the steps for forming an organic light-emittingdiode (OLED), wherein

-   -   on a substrate a first anode electrode is formed,    -   on the first anode electrode an emission layer is formed,    -   on the emission layer an electron transport layer stack is        formed, preferably a first electron transport layer is formed on        the emission layer and optional a second electron transport        layer is formed,    -   and finally a cathode electrode is formed,    -   optional a hole injection layer, a hole transport layer, and a        hole blocking layer, formed in that order between the first        anode electrode and the emission layer,    -   optional an electron injection layer is formed between the        electron transport layer and the cathode electrode.

According to various embodiments of the present invention, the methodmay further include forming an electron injection layer on a firstelectron transport layer. However, according to various embodiments ofthe OLED of the present invention, the OLED may not comprise an electroninjection layer.

According to various embodiments, the OLED may have the following layerstructure, wherein the layers having the following order:

an anode, first hole transport layer, second hole transport layer,emission layer, optional second electron transport layer, first electrontransport layer comprising a compound of formula 1 according to theinvention, optional an electron injection layer, and a cathode.

According to another aspect of the invention, it is provided anelectronic device comprising at least one organic light emitting deviceaccording to any embodiment described throughout this application,preferably, the electronic device comprises the organic light emittingdiode in one of embodiments described throughout this application. Morepreferably, the electronic device is a display device.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. However, the present disclosure is not limited tothe following examples. Reference will now be made in detail to theexemplary aspects.

Preparation of Compounds of Formula 1

Compound of formula 1 may be prepared as described below.

Synthesis of D1:

2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine

A flask was flushed with nitrogen and charged with2,4-dichloro-6-phenyl-1,3,5-triazine (100 g, 442 mmol),dibenzo[b,d]furan-3-ylboronic acid (75 g, 354 mol), Pd(PPh₃)₄(25.6 g, 22mmol), and K₂CO₃ (153 g, 1106 mmol). A mixture of deaeratedtoluene/THF/water (1:1:1, 1110 mL) was added and the reaction mixturewas heated to 65° C. under a nitrogen atmosphere for 2.5 h. The reactionmixture was cooled down to 5° C. and the precipitate was collected bysuction filtration and washed with a minimal amount of toluene. Afterwashing with water until the filtrate was pH neutral, the solid waswashed with methanol and dried. Subsequently, the solid was dissolved inhot chloroform and filtered over a pad of silica. Additional chloroformwas used to rinse the product completely. The filtrate was concentratedin vacuo to a minimal volume and n-hexane was added. After stirringovernight, the obtained precipitate was isolated by suction filtration,washed with n-hexane and dried. After purification by sublimation, 62.7g (40%) of a white solid were obtained.

2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(3-(9-phenyl-9H-fluoren-9-yl)phenyl)-1,3,5-triazine

A flask was flushed with nitrogen and charged with2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (10 g, 27.95mmol),4,4,5,5-tetramethyl-2-(3-(9-phenyl-9H-fluoren-9-yl)phenyl)-1,3,2-dioxaborolane(13 g, 29.35 mmol), Pd(PPh₃)₄ (0.65 g, 0.56 mmol), and K₂CO₃ (7.7 g,55.9 mmol). A mixture of deaerated THF/water (2:1, 150 mL) was added andthe reaction mixture was heated to reflux under a nitrogen atmospherefor 18 h. After cooling down to room temperature, the THF was removed invacuo, chloroform was added and organic phase was washed with waterthree times. The organic phase was dried over MgSO₄ and filtered over asilica pad. Additional chloroform was used to rinse the productcompletely. The filtrate was concentrated in vacuo to a minimal volumeand n-hexane was added. After stirring overnight, the obtainedprecipitate was isolated by suction filtration, washed with n-hexane anddried to yield 16.6 g (93%) of a white solid. Final purification wasachieved by sublimation. m/z=640 ([M+H]+).

Compound D2 was prepared in a similar manner. The Tg of compound D2 is134° C.

Compounds of formula 1b and 1c may be prepared via a similar route,starting from the following compounds

General Procedure for Fabrication of OLEDs

For top emission devices, Examples 1 and comparative example 1, a glasssubstrate was cut to a size of 50 mm×50 mm×0.7 mm, ultrasonicallycleaned with isopropyl alcohol for 5 minutes and then with pure waterfor 5 minutes, and cleaned again with UV ozone for 30 minutes. 100 nm Agwere deposited on the glass substrate at a pressure of 10⁻⁵ to 10⁻⁷ mbarto form the anode.

Then, 92 vol.-%Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine(CAS 1242056-42-3) with 8 vol.-%2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile)was vacuum deposited on the anode, to form a HIL having a thickness of10 nm. Then,Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-aminewas vacuum deposited on the HIL, to form a HTL having a thickness of 118nm.

ThenN,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine(CAS 1198399-61-9) was vacuum deposited on the HTL, to form an electronblocking layer (EBL) having a thickness of 5 nm.

Then 97 vol.-% H09 (Sun Fine Chemicals) as EML host and 3 vol.-% BD200(Sun Fine Chemicals) as fluorescent blue dopant were deposited on theEBL, to form a blue-emitting EML with a thickness of 20 nm.

Then the hole blocking layer is formed with a thickness of 5 nm bydepositing 2,4-diphenyl-6-(4′,5′,6′-triphenyl-[1,1′:2′,1″:3″,1′″:3′″,1″″-quinquephenyl]-3″″-yl)-1,3,5-triazine on the emission layer.

Then, the electron transporting layer is formed on the hole blockinglayer according to Examples 1 and comparative example 1 with a thethickness of 31 nm. The electron transport layer comprises 50 wt.-%matrix compound and 50 wt.-% of alkali organic complex. The compositionis shown in Table 1.

Then, the electron injection layer is formed on the electrontransporting layer by deposing Yb with a thickness of 2 nm.

Ag is evaporated at a rate of 0.01 to 1 Å/s at 10⁻⁷ mbar to form acathode with a thickness of 11 nm.

A cap layer ofBiphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amineis formed on the cathode with a thickness of 75 nm.

The OLED stack is protected from ambient conditions by encapsulation ofthe device with a glass slide. Thereby, a cavity is formed, whichincludes a getter material for further protection.

To assess the performance of the inventive examples compared to theprior art, the current efficiency is measured under ambient conditions(20° C.). Current voltage measurements are performed using a Keithley2400 sourcemeter, and recorded in V. At 10 mA/cm² for top emissiondevices, a calibrated spectrometer CAS 140 from Instrument Systems isused for measurement of CIE coordinates and brightness in Candela.Lifetime LT of the device is measured at ambient conditions (20° C.) and30 mA/cm², using a Keithley 2400 sourcemeter, and recorded in hours.

The brightness of the device is measured using a calibrated photo diode.The lifetime LT is defined as the time till the brightness of the deviceis reduced to 97% of its initial value.

The light output in external efficiency EQE and power efficiency (lm/Wefficiency) are determined at 10 mA/cm² for top emission devices.

To determine the efficiency EQE in % the light output of the device ismeasured using a calibrated photodiode.

To determine the power efficiency in lm/W, in a first step the luminancein candela per square meter (cd/m2) is measured with an arrayspectrometer CAS 140 CT from Instrument Systems which has beencalibrated by Deutsche Akkreditierungsstelle (DAkkS). In a second step,the luminance is then multiplied by π and divided by the voltage andcurrent density.

In bottom emission devices, the emission is predominately Lambertian andquantified in percent external quantum efficiency (EQE) and powerefficiency in lm/W.

In top emission devices, the emission is forward directed,non-Lambertian and also highly dependent on the micro-cavity. Therefore,the external quantum efficiency (EQE) and power efficiency in lm/W willbe higher compared to bottom emission devices.

Technical Effect of the Invention

As can be seen in Table 1, the Tg of compound of formula 1 is increasedover the Tg of comparative example 1.

Top Emission Devices

In Table 1 is shown the performance of in organic electronic devicecomprising an organic semiconductor layer comprising a compound offormula 1 and an alkali organic complex.

In comparative example 1, compound ETM-1 was used as matrix compound:

In comparative example 1, the organic semiconductor layer comprises 50vol.-% ETM-1 and 50 vol.-% LiQ. The operating voltage is 3.6 V, the cd/Aefficiency is 7.5 cd/A and the lifetime is 72 hours.

In Example 1, the organic semiconductor layer comprises 50 vol.-%compound of formula 1 D1 and 50 vol.-% LiQ. The operating voltage is 3.7V. The cd/A efficiency is improved to 8.1 cd/A and the lifetime isimproved to 142 hours.

In summary, improved cd/A efficiency and/or improved lifetime may beachieved when the organic semiconductor layer comprises a compound offormula 1.

TABLE 1 Performance data of organic electroluminescent device comprisingan organic semiconductor layer comprising a compound of formula 1 and analkali organic complex Concen- tration of alkali cd/A organic Operatingeffici- Tg of Alkali complex Thick- voltage ency at matrix organic inthe ness at 10 10 mA/ LT Matrix compound com- ETL ETL mA/cm² cm² 97compound ( ° C.) plex (wt.-%) (nm) (V) (cd/A) (h) Comp.- ETM-1 113 LiQ50 31 3.6 7.5 72 example 1 Example D1 126 LiQ 50 31 3.7 8.1 142 1

While this invention has been described in connection with what ispresently considered to be practical exemplary embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims. Therefore, the aforementioned embodimentsshould be understood to be exemplary but not limiting the presentinvention in any way.

1. A compound of formula 1,

wherein X is selected from O or S; Ar¹ is selected from C₁ to C₁₆ alkyl,substituted or unsubstituted C₆ to C₂₄ aryl or substituted orunsubstituted C₃ to C₃₆ heteroaryl; Ar² is selected from C₁ to C₁₆alkylene or is selected from unsubstituted arylene (C7) to (C11):

Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted C₆ toC₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl; andwherein Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃ toC₃₆ heteroaryl is mono or di-substituted, wherein the substituents ofthe substituted C₆ to C₂₄ aryl and substituted C₃ to C₃₆ heteroaryl areselected from C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially orperfluorinated C₁ to C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN; and wherein Ar³of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃ to C₃₆heteroaryl is mono or di-substituted, wherein the substituents of thesubstituted C₆ to C₃₆ aryl and substituted C₃ to C₃₆ heteroaryl areselected from C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially orperfluorinated C₁ to C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN.
 2. The compoundof formula 1 according to claim 1 having the formula 1a:


3. The compound of formula 1 according to claim 1 having the formula 1b:


4. The compound of formula 1 according to claim 1 having the formula 1c:


5. The compound of formula 1 according to claim 1, wherein Ar¹ issubstituted or unsubstituted C₆ to C₁₂ aryl, or substituted orunsubstituted C₃ to C₁₈ heteroaryl, wherein the substituents of thesubstituted C₆ to C₁₂ aryl and substituted C₃ to C₁₈ heteroaryl areselected from C₁ to C₁₀ alkyl or CN.
 6. The compound of formula 1according to claim 1, wherein Ar³ is selected from substituted orunsubstituted C₆ to C₂₄ aryl, wherein the substituents of thesubstituted C₆ to C₂₄ aryl are selected from C₁ to C₁₀ alkyl or CN. 7.The compound of formula 1 according to claim 1, wherein Ar¹ is selectedfrom substituted or unsubstituted annelated C₆ to C₂₄ aryl orsubstituted or unsubstituted annelated C₃ to C₃₆ heteroaryl, wherein thesubstituents of the substituted annelated C₆ to C₂₄ aryl and substitutedC₃ to C₃₆ annelated heteroaryl are selected from C₁ to C₁₆ alkyl, C₆ toC₁₈ aryl, C₃ to C₂₅ heteroaryl or CN.
 8. The compound of formula 1according to claim 1, wherein Ar³ is selected from unsubstituted C₆ toC₂₄ aryl; and Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or C₁ toC₁₆ alkyl substituted C₆ to C₂₄ aryl.
 9. The compound of formula 1according to claim 1, wherein Ar¹ and A³ are independently selected fromB1 to B53: wherein i) B1 to B6 are substituted or unsubstitutednon-heteroaryl groups:

j) B7 to B16 are substituted or unsubstituted annelated non-heteroarylgroups:

or k) B17 to B25 are dibenzofurane/dibenzothiophene group:

l) B26 to B28 are unsubstituted pyridine groups:

m) B29 to B46 are unsubstituted or substituted hetero arylene groups:

n) B47 to B48 unsubstituted annelated hetero arylene groups:

o) B49 and B50 are nitrile substituted phenyl groups

p) B51 to B53 are nitrile substituted biphenyl groups

wherein the substituent R² is independently selected from H, C₁ to C₁₆alkyl, C₆ to C₁₈ aryl.
 10. The compound of formula 1 according to claim1, wherein Ar² is selected from unsubstituted arylene (C7).
 11. Thecompound of formula 1 according to claim 1, wherein the compound isselected from D1 to D11:


12. An organic semiconductor layer comprising at least one compound offormula 1 according to claim
 1. 13. The organic semiconductor layeraccording to claim 12, further comprises a metal, metal salt or organicalkali metal complex.
 14. An organic electronic device comprising anorganic semiconductor layer according to claim 12, wherein at least oneorganic semiconductor layer comprises a compound selected from formula1, 1a, 1b or 1c.
 15. The organic electronic device according to claim14, wherein the electronic device is selected from a light emittingdevice, thin film transistor, a battery, a display device or aphotovoltaic cell.